Micropatterned Polymer Nanoarrays with Distinct Superwettability for a Highly Efficient Sweat Collection and Sensing Patch.

Wearable sweat sensor offers a promising means for noninvasive real-time health monitoring, but the efficient collection and accurate analysis of sweat remains challenging. One of the obstacles is to precisely modulate the surface wettability of the microfluidics to achieve efficient sweat collection. Here a facile initiated chemical vapor deposition (iCVD) method is presented to grow and pattern polymer nanocone arrays with distinct superwettability on polydimethylsiloxane microfluidics, which facilitate highly efficient sweat transportation and collection. The nanoarray is synthesized by manipulating monomer supersaturation during iCVD to induce controlled nucleation and preferential vertical growth of fluorinated polymer. Subsequent selective vapor deposition of a conformal hydrogel nanolayer results in superhydrophilic nanoarray floor and walls within the microchannel that provide a large capillary force and a superhydrophobic ceiling that drastically reduces flow friction, enabling rapid sweat transport along varied flow directions. A carbon/hydrogel/enzyme nanocomposite electrode is then fabricated by sequential deposition of highly porous carbon nanoparticles and hydrogel nanocoating to achieve sensitive and stable sweat detection. Further encapsulation of the assembled sweatsensing patch with superhydrophobic nanoarray imparts self-cleaning and water-proof capability. Finally, the sweat sensing patch demonstrates selective and sensitive glucose and lactate detection during the on-body test.

Deeper Insights into the Morphology Effect of Na2Ti3O7 Nanoarrays on Sodium-Ion Storage.

Na2Ti3O7-based anodes show great promise for Na+ storage in sodium-ion batteries (SIBs), though the effect of Na2Ti3O7 morphology on battery performance remains poorly understood. Herein, hydrothermal syntheses is used to prepare free-standing Na2Ti3O7 nanosheets or Na2Ti3O7 nanotubes on Ti foil substrates, with the structural and electrochemical properties of the resulting electrodes explored in detail. Results show that the Na2Ti3O7 nanosheet electrode (NTO NSs) delivered superior performance in terms of reversible capacity, rate capability, and especially long-term durability in SIBs compared to its nanotube counterpart (NTO NTs). Electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations, combined with density functional theory calculations, demonstrated that the flexible 2D Na2Ti3O7 nanosheets are mechanically more robust than the rigid Na2Ti3O7 nanotube arrays during prolonged battery cycling, explaining the superior durability of the NTO NSs electrode. This work prompts the use of anodes based on Na2Ti3O7 nanosheets in the future development of high-performance SIBs.

Machine learning-driven SERS analysis platform for rapid and accurate detection of precancerous lesions of gastric cancer.

A novel approach is proposed leveraging surface-enhanced Raman spectroscopy (SERS) combined with machine learning (ML) techniques, principal component analysis (PCA)-centroid displacement-based nearest neighbor (CDNN). This label-free approach can identify slight abnormalities between SERS spectra of gastric lesions at different stages, offering a promising avenue for detection and prevention of precancerous lesion of gastric cancer (PLGC). The agaric-shaped nanoarray substrate was prepared using gas-liquid interface self-assembly and reactive ion etching (RIE) technology to measure SERS spectra of serum from mice model with gastric lesions at different stages, and then a SERS spectral recognition model was trained and constructed using the PCA-CDNN algorithm. The results showed that the agaric-shaped nanoarray substrate has good uniformity, stability, cleanliness, and SERS enhancement effect. The trained PCA-CDNN model not only found the most important features of PLGC, but also achieved satisfactory classification results with accuracy, area under curve (AUC), sensitivity, and specificity up to 100%. This demonstrated the enormous potential of this analysis platform in the diagnosis of PLGC.

In Situ Self-Growth of a ZnO Nanorod Array on Nonwoven Fabrics for Empowering Superhydrophobic and Antibacterial Features.

ZnO nanorod nonwoven fabrics (ZNRN) were developed through hydrothermal synthesis to facilitate the prevention of the transmission of respiratory pathogens. The superhydrophobicity and antibacterial properties of ZNRN were improved through the response surface methodology. The synthesized material exhibited significant water repellency, indicated by a water contact angle of 163.9°, and thus demonstrated antibacterial rates of 91.8% for Escherichia coli (E. coli) and 79.75% for Staphylococcus aureus (S. aureus). This indicated that E. coli with thinner peptidoglycan may be more easily killed than S. aureus. This study identified significant effects of synthesis conditions on the antibacterial effectiveness, with comprehensive multivariate analyses elucidating the underlying correlations. In addition, the ZnO nanorod structure of ZNRN was characterized through SEM and XRD analyses. It endows the properties of superhydrophobicity (thus preventing bacteria from adhering to the ZNRN surface) and antibacterial capacity (thus damaging cells through the puncturing of these nanorods). Consequently, the alignment of two such features is desired to help support the development of personal protective equipment, which assists in avoiding the spread of respiratory infections.

Dual-gradient Concentration Distribution in Sb-Cu Alloy Nanoarrays for Robust Sodium-ionStorage.

Alloy-type materials are attractive for anodes in sodium-ion batteries (SIBs) owing to their high theoretical capacities and overall performance. However, the accumulation of stress/strain during repeated cycling results in electrode pulverization, leading to rapid capacity decay and eventual disintegration, thus hindering their practical applications. Herein, we report a 3D coral-like Sb-Cu alloy nanoarray with gradient distribution of both elements. The array features a Sb-rich bottom and a Cu-rich top with increasing Sb and decreasing Cu concentrations from top to bottom. The former is the active component that provides the high capacity, whereas the latter serves as an inert additive that acts against volume variation. The gradual transition in composition within the electrode introduces a ladder-type volume expansion effect, facilitating a smooth distribution and effective release of stress, thereby ensuring the wanted mechanical stability and structural integrity. The as-developed nanoarray affords a high reversible capacity (460 mAh g-1 at 0.5 C), stable cycling (89% retention over 120 cycles at 1.0 C), and superior rate capability (354 mAh g-1 at 10 C). The concentration dual-gradient strategy paves a new pathway of designing alloy-type materials for SIBs.

Surface-Initiated Living Self-Assembly of Polythiophene-Based Conjugated Block Copolymer into Erect Micellar Brushes.

Nanostructured conjugated polymers are of widespread interest due to their broad applications in organic optoelectronic devices, biomedical sensors and other fields. However, the alignment of conjugated nanostructures perpendicular to a surface remains a critical challenge. Herein, we report a facile method to directly self-assemble a poly(3-(2-ethylhexyl)thiophene), P3EHT-based block copolymer into densely aligned micellar brushes through surface-initiated living crystallization-driven self-assembly. The presence of an ethyl pendant on the side group intrinsically moderates the crystallization rate of the polythiophene main chains, and hence favors the controlled living growth of long conjugated fibers and the subsequent fabrication of conjugated micellar brushes. The corona of the micellar brush can be further decorated with platinum nanoparticles, which enables the formation of erect nanoarrays with heights up to 2700 nm in the dried state. This also renders the micellar brush catalytically active toward hydrogen evolution reaction, which shows a low overpotential of 27 mV at 10 mA cm-2 . Notably, the P3EHT-based micellar brush can simultaneously grow with polyferrocenyldimethylsilane, PFS-based micellar brush on the same surface without any significant interference between the two systems. Thus, these two micellar brushes can be patterned through site-selective immobilization of two types of seeds followed by independent living self-assembly.

3D Hierarchical-Architectured Nanoarray Electrode for Boosted and Sustained Urea Electro-Oxidation.

Exploring active and durable Ni-based materials with optimized electronic and architectural engineering to promote the urea oxidation reaction (UOR) is pivotal for the urea-related technologies. Herein a 3D self-supported hierarchical-architectured nanoarray electrode (CC/MnNi@NC) is proposed in which 1D N-doped carbon nanotubes (N-CNTs) with 0D MnNi nanoparticles (NPs) encapsulation are intertwined into 2D nanosheet aligned on the carbon cloth for prominently boosted and sustained UOR electrocatalysis. From combined experimental and theoretical investigations, Mn-alloying can regulate Ni electronic state with downshift of the d-band center, facilitating active Ni3+ species generation and prompting the rate-determining step (*COO intermediate desorption). Meanwhile, the micro/nano-hierarchical nanoarray configuration with N-CNTs encapsulating MnNi NPs can not only endow strong operational durability against metal corrosion/agglomeration and enrich the density of active sites, but also accelerate electron transfer, and more intriguingly, promote mass transfer as a result of desirable superhydrophilic and quasi-superaerophobic characteristics. Therefore, with such elegant integration of 0D, 1D and 2D motifs into 3D micro/nano-hierarchical architecture, the resulting CC/MnNi@NC can deliver admirable UOR performance, favorably comparable to the best-performing UOR electrocatalysts reported thus far. This work opens a fresh prospect in developing advanced electrocatalysts via electronic manipulation coupled with architectural engineering for various energy conversion technologies.

Defective TiO2- x for High-Performance Electrocatalytic NO Reduction toward Ambient NH3 Production.

Synthesis of green ammonia (NH3 ) via electrolysis of nitric oxide (NO) is extraordinarily sustainable, but multielectron/proton-involved hydrogenation steps as well as low concentrations of NO can lead to poor activities and selectivities of electrocatalysts. Herein, it is reported that oxygen-defective TiO2 nanoarray supported on Ti plate (TiO2- x /TP) behaves as an efficient catalyst for NO reduction to NH3 . In 0.2 m phosphate-buffered electrolyte, such TiO2- x /TP shows competitive electrocatalytic NH3 synthesis activity with a maximum NH3 yield of 1233.2 µg h-1  cm-2 and Faradaic efficiency of 92.5%. Density functional theory calculations further thermodynamically faster NO deoxygenation and protonation processes on TiO2- x (101) compared to perfect TiO2 (101). And the low energy barrier of 0.7 eV on TiO2- x (101) for the potential-determining step further highlights the greatly improved intrinsic activity. In addition, a Zn-NO battery is fabricated with TiO2- x /TP and Zn plate to obtain an NH3 yield of 241.7 µg h-1  cm-2 while providing a peak power density of 0.84 mW cm-2 .

Microarray fabrication techniques for multiplexed bioassay applications.

Microarrays are powerful tools for high-throughput bioassays that can extract information from tens of thousands of micro-spots consisting of biomolecules. This information is invaluable to many applications, such as drug discovery and disease diagnostics. Different applications of these microarrays need spots of different shapes, sizes, and chemistries to achieve their goals. Micro/nano-fabrication techniques are used to make microarrays with different feature structures and array densities for required assay procedures. Understanding these fabrication methods is essential to creating an effective microarray. The purpose of this article is to critically review fabrication methods used in recent microarray-based bioassay studies. We summarized commonly used microarray fabrication techniques and filled the gap in recent literature on relevant topics. We discussed recent examples of how microarrays were fabricated and used in a variety of bioassays. Specifically, we examined microarray printing, various microlithography techniques, and microfluidics-based microarray fabrication. We evaluated how their application shaped the fabrication methods and compared their performance based on different applications. In the end, we discussed current challenges and outlined potential future directions. This review addressed the gap in literature and provided important insights for choosing appropriate fabrication techniques towards different applications.

Positional control of DNA origami based gold dimer hybrid nanostructures on pre-structured surfaces.

This study explores important parameters for achieving a high-level positional control of DNA-nanoparticle hybrid structures by drop-casting onto a pre-structured silicon surface, in which the active adsorption sites were defined using electron beam lithography. By confining the adsorption sites to the scale of the DNA origami, we create multi-dimensional patterns and study the effect of diffusion and hybrid nanostructure concentration in the liquid on site occupation. We also propose a physical diffusion model that highlights the importance of surface diffusion in facilitating the adsorption of hybrid nanostructure onto active sites, particularly for two and one-dimensional adsorption sites. Our study shows prominent results of the hybrid nanostructure's selective adsorption, indicating high adsorption efficiency and precise control over the position, as well as the spatial orientation. We anticipate similar results in related systems, both in terms of different surfaces and similar DNA structures. Overall, our findings offer promising prospects for the development of large-scale nanoarrays on micrometer-scale surfaces with nanometer precision and orientation control.

A Hierarchical CuO Nanowire@CoFe-Layered Double Hydroxide Nanosheet Array as a High-Efficiency Seawater Oxidation Electrocatalyst.

Seawater electrolysis has great potential to generate clean hydrogen energy, but it is a formidable challenge. In this study, we report CoFe-LDH nanosheet uniformly decorated on a CuO nanowire array on Cu foam (CuO@CoFe-LDH/CF) for seawater oxidation. Such CuO@CoFe-LDH/CF exhibits high oxygen evolution reaction electrocatalytic activity, demanding only an overpotential of 336 mV to generate a current density of 100 mA cm-2 in alkaline seawater. Moreover, it can operate continuously for at least 50 h without obvious activity attenuation.

A miniature CuO nanoarray sensor for noninvasive detection of trace salivary glucose.

An ultrasensitive mini-sensor has been developed for nonenzymatic and noninvasive determination of trace glucose in saliva. The miniature detector exhibits ultra-high sensitivity and resolution at very low glucose concentration owing to the excellent electrocatalytic activity and electron transfer rate of the prepared 3D ordered CuO nanoflake array in-situ grown on a copper foil. The structure and morphology of the cupric oxide nanoarray were characterized by X-ray powder diffraction and scanning electron microscopy. The electrocatalysis of the CuO nanoarray modified electrode to glucose was demonstrated by cyclic voltammetry and chronoamperometry. The modified electrode presents a high sensitivity of 4954 µA mM-1 cm-2 to glucose at + 0.55 V with a wide linear range of 1.0 µmol/L to 6000 µmol/L and a low detection limit of 0.1 µmol/L and long-term stability. Furthermore, the mini-sensor can clearly distinguish diabetics from healthy people because of its excellent sensing performance. The developed miniaturized sensor holds the prospect for noninvasive determination of trace glucose in saliva for diabetic patients.

Phase separation enabled silver nano-array.

The surface-supported silver nanoparticles have been studied and applied in various applications. Many unique nanostructures have been introduced into this field to improve the functionalities of the surfaces depending on application purposes. We created featured silver nano-array surfaces by utilizing the solvent-mediated phase transition on the surface grafted with poly (acrylic) acids polymer chains and taking advantage of the low temperature of argon gas discharged plasma as a reducing agent. The applied solvents and grafted polymer chain densities affected the phase transition and thus determined the outcome of surface nano-array patterns. However, the total loaded silver ions on the surface affected silver nano-array structures at the sub-micron levels. The featured silver patterned surfaces made in the optimal conditions present a favorable surface-enhanced Raman spectroscopy enhancement as well as recyclability for detection re-usage. This novel method prepares tunable silver nanopatterned surfaces and provides a new approach to various potential applications.

Systematic Design of a Flow-Through Titanium Electrode-Based Device with Strong Oil Droplet Rejection Property for Superior Oil-in-Water Emulsion Separation Performance.

Oily wastewater treatment has been restricted by the existence of stable oil-in-water (O/W) emulsions containing micrometer-sized oil droplets. However, the strong adhesion and stacking of emulsified oil droplets on the surface of current separation media cause serious fouling of the treatment unit and the rapid decline of treatment efficiency. Herein, a novel flow-through titanium (Ti) electrode-based filtration device with remarkable oil droplet rejection property was well designed for the continuously separating O/W emulsion. In contrast to the pristine Ti foam, the permeance of the TiO2 nanoarray-coated Ti foam (NATF) increased from 2538 to 4364 L m-2 h-1 bar-1 through gravity-driven flow. Further, more than ∼70% permeability can be maintained after 6 h of O/W emulsion filtration using the current device, the value of which was markedly higher than that of conventional oil/water separation filters (less than 5%). According to the results of wettability test, the super-oil-repellent surface endowed by this nanoarray structure primarily avoided the formation of a compact oil fouling layer. When the voltage was applied, accompanied by the electrophoresis effect, redistribution of surfactant molecules on the surface of oil droplets induced by an electric field made them readily captured by the microbubbles continuously generated from the electrode, thereby rapidly migrating these bubble-adhered oil droplets far from the filtration medium.

Photoelectrochemical determination of diclofenac using oriented single-crystalline TiO2 nanoarray modified with molecularly imprinted polypyrrole.

A novel molecular imprint photoelectrochemical (PEC) sensor has been prepared based on oriented single-crystalline TiO2 nanoarray (TNA) material for sensitive detection of diclofenac (DCF). The TNA obtained by the one-step hydrothermal method was characterized by XRD, SEM, and TEM. Polypyrrole film was formed on the TNA by electrochemical method, and DCF was imprinted on the polymer film as the template molecule. After the removal of DCF, there appeared lots of specific recognition sites that matched template molecules. The experimental results demonstrated that the constructed PEC sensor has good sensitivity and selectivity for the detection of DCF, which can be attributed to the high photoelectric conversion efficiency of TNA and the high selectivity of molecular imprinting technology. The fabricated PEC sensor showed a wide detection range (0.05-1000 µM) and a low limit of detection (0.0034 µM) for DCF, as well as good repeatability and stability. The proposed PEC sensor provided an effective strategy in the monitoring of environmental pollutants.

A Hierarchical Anodic Aluminum Oxide Template.

Anodic aluminum oxide (AAO) templates are widely used for the development of various functional nanomaterials due to their highly ordered and tunable porous structures. Here, we report a new hierarchical AAO (hAAO) template with the hexagonally ordered unit cells and the radially distributed nanochannels. It is formed by integrating the self-assembled polystyrene microsphere template into the AAO fabrication process and rationalized in terms of mechanical stress and electric-field-induced oxide dissolution. The back side of the hAAO template resembles a moth-eye-like nanoarray, which shows good hydrophobicity. A variety of radial nanopillar arrays and moth-eye-like nanoarrays are fabricated by a series of materials and synthesis techniques employing the hAAO template. These unique nanoarrays demonstrate many physicochemical properties that are distinct from those obtained from the conventional AAO template.

Fabrication of Nanoscale Gas-Liquid Interfaces in Hydrophilic/Hydrophobic Nanopatterned Nanofluidic Channels.

Gas-liquid interfaces (GLIs) are ubiquitous and have found widespread applications in a large variety of fields. Despite the recent trend of downscaling GLIs, their nanoscale fabrication remains challenging because of the lack of suitable tools. In this study, a nanofluidic device, which has undergone precise local surface modification, is used in combination with tailored physicochemical effects in nanospace and optimized nanofluidic operations, to produce uniform, arrayable, stable, and transportable nanoscale GLIs that can concentrate molecules of interest at the nanoscale. This approach provides a delicate nanofluidic mechanism for downscaling gas-liquid interfaces to the nanometer scale, thus opening up a new avenue for gas-liquid interface studies and applications.

Nanoarray Structures for Artificial Photosynthesis.

Conversion and storage of solar energy into fuels and chemicals by artificial photosynthesis has been considered as one of the promising methods to address the global energy crisis. However, it is still far from the practical applications on a large scale. Nanoarray structures that combine the advantages of nanosize and array alignment have demonstrated great potential to improve solar energy conversion efficiency, stability, and selectivity. This article provides a comprehensive review on the utilization of nanoarray structures in artificial photosynthesis of renewable fuels and high value-added chemicals. First, basic principles of solar energy conversion and superiorities of using nanoarray structures in this field are described. Recent research progress on nanoarray structures in both abiotic and abiotic-biotic hybrid systems is then outlined, highlighting contributions to light absorption, charge transport and transfer, and catalytic reactions (including kinetics and selectivity). Finally, conclusions and outlooks on future research directions of nanoarray structures for artificial photosynthesis are presented.

Enhanced Concanavalin†A Binding to Preorganized Mannose Nanoarrays in Glycodendrimersomes Revealed Multivalent Interactions.

The effect of the two-dimensional glycan display on glycan-lectin recognition remains poorly understood despite the importance of these interactions in a plethora of cellular processes, in (patho)physiology, as well as its potential for advanced therapeutics. Faced with this challenge we utilized glycodendrimersomes, a type of synthetic vesicles whose membrane mimics the surface of a cell and offers a means to probe the carbohydrate biological activity. These single-component vesicles were formed by the self-assembly of sequence-defined mannose-Janus dendrimers, which serve as surrogates for glycolipids. Using atomic force microscopy and molecular modeling we demonstrated that even mannose, a monosaccharide, was capable of organizing the sugar moieties into periodic nanoarrays without the need of the formation of liquid-ordered phases as assumed necessary for rafts. Kinetics studies of Concanavalin A binding revealed that those nanoarrays resulted in a new effective ligand yielding a ten-fold increase in the kinetic and thermodynamic constant of association.

Electrochemical assay of ampicillin using Fe3N-Co2N nanoarray coated with molecularly imprinted polymer.

Self-supported Fe3N-Co2N nanoarray with high electric conductivity and large surface area was prepared for growth of MIPs and further constructing a sensitive and stable electrochemical sensor. For the evaluation of its performance, Fe3N-Co2N is used as sensing electrode material, and AMP is used as template molecule to construct the MIP electrochemical sensor. Under the optimized conditions, the developed MIPs electrochemical sensor detects AMP with a low detection limit of 3.65 × 10-10 mol L-1 and shows outstanding reproducibility and stability. When the MIPs electrochemical sensor was applied to detect AMP in milk samples via standard addition method, the recovery within 97.06-102.43% with RSD of 1.05-2.11% was obtained. The fabrication of MIPs electrochemical sensor is highly promising for sensitive and selective electrochemical measurement and food safety testing. This work can provide theoretical guidance for truly challenging problems. Graphical abstract Principle diagram of MIP-EC sensor for detecting AMP Molecular imprinted polymers (MIPs) are widely performed for construction of electrochemical (EC) sensors especially for detecting small molecules in complex environment. However, the large-scale and robust preparation of MIPs in situ on sensor platform limits their practical applications. We fabricated a MIPs EC sensor based on Fe3N-Co2N in situ grown on carbon cloth (CC) as the substrate platform (Fe3N-Co2N/CC) combining with MIPs as the target recognition element for the label-free detection of AMP. Under the optimal conditions, the developed MIPs EC sensor can detect AMP with a low detection limit of 3.65 × 10-10 mol L-1. When the AMP in milk is detected by the proposed EC sensor, it shows ideal results. Therefore, the use of self-supported Fe3N-Co2N nanoarray as the platform for the fabrication of MIPs EC sensors is highly promising for sensitive and selective EC measurement and point-of-care testing.